@article{Qian2025, 
author = {Ruru Qian and Tingting Jiang and Mengyuan Tu and Qianli Zhang and Ling Chen and Xuejiao Yang and Haizhu Yu and Manzhou Zhu},
title = {Epoxide C–O bond activation intrigued by waisted flexibility of the Au13Ag12 clusters},
year = {2025},
journal = {Nano Research},
volume = {18},
number = {9},
pages = {94907629},
keywords = {CO2, cycloaddition, atomic precision, alloy nanoclusters, epoxide},
url = {https://www.sciopen.com/article/10.26599/NR.2025.94907629},
doi = {10.26599/NR.2025.94907629},
abstract = {The atomic precision of the coin metal nanoclusters lays the foundation for the elucidation of the structure-property correlations at the atomic/molecular level. Herein, the bi-icosahedral [Au13Ag12(PPh3)10Cl8]PF6 and [Au13Ag12(PPh2Py)10Cl8]PF6 (loaded on activated carbon) have been developed as the catalyst for the epoxide cycloaddition with CO2. The [Au13Ag12(PPh2Py)10Cl8]/AC catalytic system shows better performance than its PPh3-analogue, with turnover number (TON) reaching 3.03 × 104. Specifically, the catalyst shows high substrate tolerance, and is widely applicable to different epoxide substrates bearing aryl, alkyl, halogen, alkenyl and ether groups (yield: 72%–96%). The mechanistic investigation with ultraviolet–visible absorption spectroscopy (UV–Vis), X-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance spectroscopy (NMR), cyclic voltammetry (CV) and density functional theory (DFT) calculations indicate that both the waisted coordination flexibility and pyridine N atom are important: the electron transfer from epoxide to the electrophilic, waisted Ag center drives the entire reaction, and the pyridyl N-atoms facilitates the CO2-migration and the subsequent cycloaddition processes. This study proposes the possibility for utilizing structural flexibility of metal nanoclusters as an efficient strategy to activate the substrates, which could hopefully benefit the development of more catalytic systems.}
}